Method of refining hydrocarbon liquids



Dec. 14, 1943. A M BQNOTTQ 2,336,589

METHOD OF REFINIG HYDROCARBON LIQUIDS Filed Oct. 29, 1941 5 Sheets-Sheet 1 Dec. 14, 1943. M, BONOTTQ 2,336,589

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O'FFCE METHD F REFNING HYDROCARBON LIQUIDS Michele Bonotto, rrinceton, N. J., assignor to Dorothy Di Frasso, Beverly Hills, Calif.

3 Claims.

This invention relates to improvements in processes for reiining hydrocarbon liquids used for motor fuel or solvent, such as gasoline, lnaphtha and the like, and utilizing the refined liquid.l

Certain grades of motor fuels now on the market contain more or less soluble gums, resins and other heavier undesirable components and it has been found that these motor fuels, when mixed with air in conventional proportions and ignited in the cylinder of an internal combustion engine, contribute to the production, under oonventional conditions, of what has come to be known as a fuel knock in contradistinction to a mechanical knock.

Also, because of incomplete combustion, these gums, resins and heavier constituents produce a sediment and incrustation in and on the walls of the explosion chamber and other parts of an internal combustion engine and also causes smoke in the exhaust pipe.

One of the objects of this invention is to produce a hydrocarbon liquid from which the soluble gums, resins and other heavier undesirable components have been rendered insoluble and removed and thus to provide a motor fuel or solvent having a low content of such components.

Another object of my invention is to produce, at a relatively low cost, a hydrocarbon liquid that will be free from the undesirable ingredients hereinabove referred to to such an extent as to provide a motor fuel that, when mixed with air in any conventional proportion and ignited in the cylinder of internal combustion engine, will be completely burned Without smoke and Without leaving an insulating lm, coating or deposit in or on the combustion chambers or cylinders, valves and valve stems, or spark plug points.

Another object of my invention is to produce such a treated hydrocarbon liquid that will have increased susceptibility to tetra ethyl lead over the untreated liquid so that by the addition of tetra ethyl lead uid to my treated hydrocarbon liquid, a motor fuel may be produced of higher octane rating than would be possible with the same liquid without treatment.

Another object of my invention is to provide an economical process for the continuous treatment of hydrocarbon liquids of the type hereinabove specied for the purpose of removing gums, resins or other heavier undesirable components and thus to refine or purify such hydrocarbon liquids.

Another object of my invention is to provide a process that may be carried out at room temperatures in simple and inexpensive apparatus.

Another object of my invention is to nely divide a quantity of gasoline to be treated into small droplets to enable treatment of the same with small amounts of suitable chemicals by providing better contact in the presence of water, between the hydrocarbon droplets or particles and the treating chemicals, and in the preferred embodiment of my invention, I utilize a mixture comprising a high disperson of Water in gasoline or `an emulsion of water and gasoline preferably in the proportion of three parts of gasoline to one part of water.

Another object of my invention is to subject the highly dispersed or divided gasoline droplets or particles to treatment by two groups of chemicals, the first group comprising hydroxides of heavy metals such as lead, iron, copper, zinc, silver, nickel and also aluminum hydroxide, and the second group comprising strong alkalies such as sodium, potassium, barium `or ammonium hydroxides and I have found that an eicient and economical method of utilizing the metallic hydroxides is to employ the same in solutionrin strong alkalies, such as sodium, potassium, barium or ammonium hydroxides, and where it is found more economical, I dissolve the metallic oxide in a solution of the hydroxide of the strong alkali.

Another object of my invention is to utilize a process in which the gums and other heavier components may be treated in the presence of Water with a precipitating agent, such as hydroxides of any of the metals of the iirst group which are soluble or may be caused to be soluble in Water, or which are capable of being suspended in water.

Another object of my invention is to provide a method in which a metallic hydroxide of the iirst group is associated with one or more of the above specied strong alkalies in order to produce a higher percentage of precipitation of the soluble gums, resins and like heavier cornponents at room temperature and to produce a precipitate which I believe to be a saponied product comprising a complex of soaps.

Another object of my invention is to provide a method in which two or more metallic hydroxides of the first group are associated with one of the above specied strong alkalies to produce, as hereinabove speciiied, a higher percentage of precipitation and what I believe to be a mixture of soaps.

Still another object of my invention is to produce a motor fuel that has been subjected to Figs. 1, 1f* and 1b are diagrammatic views of a batch system apparatus capable of carrying out my invention;

Fig. 2 is another diagrammatic view of, my preferred form of apparatus for carrying out my invention as a continuous System and comprising horizontally disposed units; and

Fig. 3 is a similar diagrammatic view showing a. modified form of continuous system employing vertically disposed units.

Referring now to these drawings and more particularly to Fig. 1 which illustrates a form of a10- paratus suitable for carrying out my invention in accordance With a batch system and when I employ as the treating ingredients lead hydroxide and sodium hydroxide, I may proceed as follows: First I dissolve eighty (80) grams of sodium hydroxide in 300 cubic centimeters of water in a separate container; then I heat this solution in said container to the boiling point and add. little by little, twenty-five (25) grams of lead oxide (PbO) and agitate the combined ingredients until the lead oxide is fully dissolved. To this solution, I then add in said container 1000 cubic centimeters of water. The gasoline to be treated is introduced into a mixing tank I which, in the particular embodiment heretofore used, was twenty (20) inches in diameter and four feet high and was provided with a centrally disposed shaft 2 having mounted thereon within the tank agitating paddles 3. The said shaft 2 is suitably mounted in said tank and, as shown, is mounted at its bottom portion in a bearing 4 supported at the bottom of the tank and extends through a stuffing box 5 supported in the cover I' of the tank, the said shaft being also supported outside the tank above the cover in a bearing 6 elevated from the cover of the tank by a spider '1. The shaft 2 may be revolved by any suitable power, and, as shown, is provided with a motor 8. The gasoline is introduced into the tank through any suitable pipe or opening Ib and I then add to said gasoline, water in a quantity preferably amounting to one-fourth (1A) of the volume of gasoline, this proportion of water and gasoline being economical, though I may, if desired, use any suitable lesser or greater proportion of water. The agitating paddles are then revolved through the shaft 2 at approximately 600 R. P. M. and I nnd that after 30 to 45 seconds the dispersion of the water in gasoline has reached a point sufficient to permit continuation of the treatment. I then add to the highly dispersed Water in gasoline, a quantity of the prepared solution described above amounting to from twoor four cubic centimeters per gallon of gasoline, and this prepared solution is introduced by drops or spraying to the mixing drum during the running and agitation of the dispersed liquids therein. After a period of from to 30 seconds, I notice that a thickening of the dispersed liquids or emulsion has taken place and the process is completed. I then stop the machine and the dispersion or emulsion on such stoppage separates into three layers, the bottom layer being water, the middle layer comprising a occulent precipitate and the top layer comprising purified gasoline. By any conventional means I may then decant or remove the gasoline or, if desired, the mixture may be conducted to a centrifuging machine and the purified gasoline may be thus separated from the water'and flocculent precipitate.

In Fig. 2 which illustrates a preferred form of apparatus for carrying out my invention as a continuous system, I have shown the supply of gasoline to be treated stored in a tank Ill, the water to be used is stored in a tank II and the prepared chemical solution described above in a tank I2, while the treating apparatus comprises a horizontally-disposed cylindrical drum I3, provided with an axially disposed shaft I4 having mounted thereon paddles I5 revolved by a motor I6. The shaft is, of course, suitably supported in bearings and provided with a conventional stuffing box. The tank I3 has a gasoline inlet I3 and water inlet I3a arranged at the forward end of the tank and is provided at its rear end with a baiiie I6. The gasoline from tank I8 is fed through pipe I0' to the treating drum and the water is fed through pipe I I' from the water tank II, these liquids being so fed preferably in proportion of one fourth (1A) of a unit of water to three-fourths (3A) of a unit of gasoline, it being understood that suitable proportioning devices Illa and II are provided in the pipes I0 and II' to enable proper proportions of gasoline and water to be supplied to the drum I3. In this embodiment of the invention, the motor I6 continuously revolves the shaft I4 and the water and gasoline are immediately mixed in proper dispersion or emulsion, the time of 30 to 45 seconds or duration of agitation required to produce this emulsion is occupied by providing a drum of suitable capacity and length and utilizing a baille of suitable height as well as by providing a proper number of paddles or other agitating devices in relation to the capacity of the drum. In this embodiment, the vvatel` in gasoline is highly dispersed and such highly dispersed immiscible liqnids pass over the bailie I5 and are then conducted through a rear chamber I3b and through a pipe or conduit I1 to the treating drum I8. A pipe I2' provided with a suitable proportioning device I2a, and leading from the chemical storage tank I2 is connected with this treating drum at its forward end to conduct a properly proportioned supply of chemicals thereto. The dispersed solution of water in gasoline is thus caused to mingle at this point with a solution of the chemicals which are preferably sprayed by a nozzle I 2h into said treating drum. The treating drum I8 is also provided with a shaft I9 having mounted thereon paddles 20 and being revolved by a motor 2 I. In the tank I8, the chemicals are thoroughly mixed with the dispersion of Vwater in gasoline and within 15 to 30 seconds after the addition of the chemicals hereinabove specified there occurs a thickening of the emulsion hereinabove referred to in regard to the batch system. The continuous revolution of the shaft I9, however, earries the thickened liquid over the baffle 2| mounted at the rear end of the drum. The thickened emulsion thus drops through the rear compartment I 8 and it is then conducted by pipe 22 into a surge tank 23 from which it is then conducted by conduit 24 to a centrifuging machine 25 in which the purified gasoline is separated from the water and passes out from a conduit 26 while the Water and ilocculent material passes out through the conduit 21. The flocculent material may then be further separated from the Water by settling or by a second centrifuging operation. This completes the process. In case a metallic hydroxide is used alone, as hereinabove suggested, this metallic hydroxide may be added in the form of a spray to the liquid in the second drum in the same manner as the prepared solution referred to, or said metallic hydroxide may, if desired, be added in powdered form through a suitable rotary powder-feedingv valve.

It will be seen that this process is entirely continuous and can be carried out in a highly economical manner In the preferred proportioning of the gasoline and Water and chemicals, I utilize three gallons of gasoline per minute to one gallon of water per minute, and during this time I add to the dispersed gasoline and water a quantity amounting preferably to nine (9) cubic centimeters per minute of the solution hereinabove specified in the description of my batch system. It will be understood that the dispersion or emulsion of gasoline causes the same to be nely-subdivided and presents larger contact surface for treatment by the chemical.

In Fig. 3 I have shown a modied form of a continuous system capable of carrying out my invention with vertically disposed units. In this apparatus, I have shown a gasoline storage tank 30 for the gasoline to be treated, a storage tank 3l for the water to be used in the process and a storage tank 32 for the storage of the prepared chemical solution. The mixing apparatus comprises vertically-disposed tanks provided with mixing devices. As illustrated, a vertically-disposed cylindrical tank 33 is provided with an axially-disposed shaft 33e having mounted thereon paddles 33f which are revolved by =a motor 36 through a medium of beveled gears 35'. The shaft is suitably supported at the bottom of the tank 33 in conventional bearings 33 and passes through a conventional stuffing box 33a mounted at the top of said tank. A gasoline inlet 33b and a Water inlet 33c are arranged at the bottom of the tank and its upper end has an outlet 33d for the mixed and dispersed liquids. In carrying out my process, the gasoline from the tank 30 is fed through the pipe 30' to the treating tank 33 and Water is fed from the water storage tank 3l through the pipe 3l to said treating tank, the liquids being so fed preferably in the proportions of one-quarter (1/4) of a unit of water and threequarters (3A) of a unit of gasoline, it being understood that suitable proportioning devices 30a, 3W are provided-in the pipes 30', 3l to enable proper proportions of gasoline and water to be supplied to the 'tank 33. In this apparatus, the motor 33 continuously revolves the shaft 33e and the water and gasoline are immediately mixed in proper dispersion or emulsion, the time of 30 to 45 seconds, which is the preferred duration of agitation required to produce this proper dispersion or emulsion being occupied by providing a tank of suitable capacity and height with a proper number of paddles or other agitating devices in relation to the capacity and height of the tank. In said apparatus, the Water in gasoline is highly dispersed, and such highly dispersed immiscible liquids pass through the outlet 33d and are conducted by pipe 34 through a dispersion inlet 35 located adjacent to the bottom of a tank 35. In the instant apparatus, the wall of the tank between the bottom thereof and the outlet opening 33d takes the place of the bafe I6 of Fig. 2. The pipe 34 is provided with a suitable cut-oli' valve 34 and in the said apparatus shown, a by-pass conduit 34a is connected at one end with the bottom of the tank 33 and at its other end is connected to the pipe 34 which also is provided with a conventional cut-off valve 34h. In the apparatus illustrated, as the dispersed liquids are fed into the tank 35 through the outlet 35 adjacent to the'bottom thereof, a supply of chemical is sprayed through the nozzle 31 arranged at sub stantially the same level and mixes with the dispersed liquids as they rise in thev tank 35, it being understood that the pipe 32' which conducts the chemicals from the chemical storage tank 32 `to the treating tank 35 is provided with a proportioning device 32a and thus feeds chemicals in proper proportion to the nozzle 31 under a suitable pressure to spray the same into the tank 35. Said conduit or pipe 32' also is provided, as shown, with a usual or conventional cut-off valve 32h. The dispersed solution of gasoline and water is thus caused to mingle and to be partially mixed at the lower portion of the tank with the solution of the chemicals conducted through said pipe 32 and sprayed, as aforesaid, by the nozzle 31 into said treating tank and is preferably further :and more intimately mixed by a suitable mixing means as the combined dispersion and chemicals rise in said tank. For this purpose, the treating tank 35 is also provided with a shaft 38 having mounted thereon paddles 39 revolved by a motor 40 through the beveled gears 40. During the mixing operation in the tank 35, and Within l5 to 30 seconds after addition to the dispersion of W-ater in gasoline of the chemicals hereinabove specified, there occurs a thickening of dispersion in the same manner as hereinabove referred to. Continuous revolution of the shaft 38 keeps this mixture and the thickened portions thereof in suspension, and the thickened mixture is carried upwardly until it finally reaches'the outlet 4 I, and is then conducted through the pipe or conduit 42 to a surge tank and centrifugal separator (not shown) such as hereinabove described in relation to Fig. 2. As illustrated, the tank 35 is provided with a by-pass 43 connected at one end to the bottom of said tank 35 and at the other end with the pipe 42 and said tank 35 is also preferably provided with a drain pipe 44 having a conventional cut-ofi valve 44.

In the centrifuging machine referred to, the purified gasoline is separated from the Water and passes out through one conduit While the Water and flocculent material pass out through another. The occulent material may then, as aforesaid, be separated from the Water by a second centrifuging operation, if desired. This completes the process. In case a metallic hydroxide is used alone, as hereinabove suggested, such metallic hydroxide may be added in the formof a spray to the liquids in the tank 35 in the same manner as the prepared solution referred to or said metallic hydroxide may, if desired, be added in powdered form through a suitable rotary powderfeeding valve.

In said Fig. 3, I have shown the tanks 33 and 35 connected by pipes 45 and 43 respectively to reflux condensers 41 and 48 of conventional type.

In other respects this embodiment is similar to that shown in Fig. 2.

Having described my invention, I claim:

1. A method of refining and utilizing hydrocarbon liquids containing soluble gums, resins and heavier components consisting in providing a dispersion of such hydrocarbon liquid in water, then treating the Vdispersed liquid hydrocarbon with a solution of a metallic hydroxide in an aqueous solution of a strong alkali adapted to render the gums, resins and heavier components insoluble in said liquid hydrocarbon, and then separating such insoluble components and Water from the hydrocarbon liquid. Y

2. A method of refining and utilizing hydrocarbon liquids containing soluble gums, resins and heavier components consisting in providing a dispersion of such hydrocarbon liquid in Water, then treating the dispersed liquid hydrocarbonwith a lead oxide in solution in a strong alkali adapted to render the gums, resins and heavier components insoluble in said liquid hy-l drocarbon, and then separating such insoluble components and Water from the hydrocarbon liquid.

3. A method of rening and utilizing hydrocarbon liquids containing` soluble gums, resins and heavier components consisting in providing a dispersion of such hydrocarbon liquid in Water, then treating the dispersed liquid hydrocarbon with a lead hydroxide in solution ina strong alkali adapted to render the gums, resins and heavier components insoluble in said liquid hydrocarbon, and then separating such insoluble components and Water from the hydrocarbon liquid. l

MICHELE BONOTTO. 

